Laying (linked) pentagonal tiles - trouble snapping
You can get there using vertex snapping and some manual rotation.  


Make your base tile a single face pentagon. Remove double vertices (there are some).
Don't use object instances yet, you'll convert them all in the end. Just copy new tiles now.
The main angle is 71°. Type the equations directly into the rotation field.
Enable Vertex Snapping > Median. Origin points will now snap to vertices.
Put your origin to different vertices if needed.  


Convert tiles into instances


Select all objects and go Object > Set Origin > Origin to Geometry. This will keep them in place.
Select all tiles and turn them into instances Object > Make Links > Object Data


The main face angle is 71°



Type equations into the Z rotation field.



Use Vertex Snapping > Median to snap origin point to vertices. Move the origin point if needed.



Make all tiles into instances of one. But make their origin points centered first.